Readily combustible plastic material



Patented July 23,1946

UNITED STATES PATENT OFFICE} READILY COMBUSTIBLE PLASTIC MATERIAL Herman A. Bruson and George B. Butler, Philadelphia, Pa., assignors to Rohm & Haas Company, Philadelphia, Pa., a corporation of Delaware wherein R is a nitroor polynitro-hydrocarbon radical from a monohydric nitroalcohol containing at least one nitro group for each four carbon atoms present therein and R is the hydrocarbon residue of a pry-unsaturated primary aliphatic alcohol.

The above nitro esters polymerize upon exposure to heat, light, air, and/or catalysts such as benzoyl peroxide to form transparent plastics varying from hard, glassy masses to tough, somewhat elastic, rubbery materials.

These new plastics burn in the air with great vigor and possess explosive properties. They are useful for the preparation of explosives, rockets, fuses, flares, and the like, as combustible binders or plasticizers for gun-cotton, TNT, picric acid, and other explosive compositions.

As a monohydric nitroalcohol, there may be used 2-nitroethanol-1, 2-nitro-propanol-1, 2-nitrobutanol-l, 2-nitro-2-methyl propanol-l, l-dinitrophenyl-2-nitro-2-methyl propanol-l, l-trinitrophenyl-2-nitro-2-methy1 propanol-l, 2,4,6- trinitrophenylethanol, and other monohydric alcohols in which there is present at least one nitro group for each four or fewer carbon atoms.

As a a -unsaturated primary aliphatic alcohol, there may be used allyl, methallyl, propenyl, or crotyl alcohol, or methyl-vinyl carbinol, or the like.

The dibasic carboxylic nucleus may be obtained from maleic or fumaric acids or their acyl halides or from maleic anhydride.

The new esters of this invention are readily obtainable in several ways. For example, maleic anhydride can be first esterified with a nitroalcohol corresponding to group R and the resulting half ester subsequently esterified with the unsaturated alcohol, R'OH, or the reverse procedure may be followed.

According to another procedure, the acid chloride of the half ester of one alcohol is condensed with the other alcohol.

Although the esters may be prepared in the absence of solvents other than the reactants themselves, it is preferred that a solvent be used. Suitable for this purpose are chlorinated solvents, such as carbon tetrachloride or ethylene dichloride; hydrocarbons, such as naphtha, ben- No Drawing. Application January 21, 1944,-

7 Serial No. 513,197

4 Claims. (01. 200-l8) 7 1 w c 2 zene, toluene,-or xyleneyor ethers, such as isopropyl ether, butyl ether, or the like, or mixtures of such solvents.

The esterifications involved may be performed Within the range of 50 C. to 150C; although both somewhat lower and higher temperatures may be used, depending upon reactants, solvents, etc.

There may be used in the .reaction mixture polymerization inhibitors, such as hydroquinone, pyrogallol, B-naphthol, etc. g

The following examples illustrate this invention: a

] 7 Example 1 A mixture of 78 grams (0.5 mol) ofmaleici acid mono-allyl ester, grams (0.5 mol) of 2-nitro l-butanol, .150 cc. of dry benzene, and 0.5 cciof concentrated sulfuric acid was boiled under a reflux condenser attached to a water separator for five hours, until no more water collected in the trap. After the mixture had been cooled, five grams of powdered anhydrous sodium'carbonate was added and the mixture stirred for one hour at room temperature. The mixture was filtered and the clear filtrate evaporated to'dryness in vacuo. vacuo. The allyl Z-nitrobutyl maleate distilled over at 156 -163 C./2-3 mm. a a pale yellow oil. It serves as a colloiding agent for guncotton and can also be polymerized to a transparentplastic on heating with 1-2% of benzoyl peroxide at -1 00 C.

Example 2 at C. It may also be copolymerized. with an equal weight of di-(-2-nitro-2-methyl propyl)- The residual oil was then distilled in maleate in the presence of 2% by weight of benzoyl peroxide to a combustible polymer.

Example 3 A mixture consisting of 78 grams of maleic acid mono-allylester, .53 grams of 1-nitro.-'-propano1-2, 150 cc. of benzene, and one gram of concentrated sulfuric acid was boiled under reflux for eight: hours while the water formed was continually removed by a water separator.

with water and the solvent distilled off. The residual oil was distilled in vacuo to yield allyl lnitro-isopropyl maleate CHzNOg CH5-CHO-C -oH=oHoo0-0H-.-oH=oH as a pale yellow oil which boiled at 160 C./2 mm. When heated at 100 C. with 12% by weight "of benzoyl peroxide, it polymerized to a darkbrown, thermoplastic, readily combustible resin.

Example 4 By using 0.5 mol of maleic acid mono-methallyl ester in place of the maleic acid mono-allyl ester in Example 2, the corresponding methallyl 2-nitro-Z-methyl propyl maleate is obtained as a colorless oil which boils at 158-159 C./12 mm. when heated with 2% by weight of benzoyl peroxide at 95-100 C., it polymerized to a clear, yellowish, combustible plastic.

Example 5 A mixture of 0.5 mol each of 2-nitro-2-methyl propanol and maleic acid monopropargyl ester in 150 cc. of benzene was boiled in the presence of 0.5 cc. of concentrated sulfuric acid for five to six hours under a reflux condenser attached to a Water trap. After it Was washed and dried, the product was distilled in vacuo to yield 2-nitro-2- methyl propyl propargyl maleate CHs CHs-(E-CHr-OCO-CH=CHCOO-CH2CECH N02 as a colorless oil which boiled at l45-155 C./2-3

A sample of the oil was mixed with 2% by weight of benzoyl. peroxide and polymerized at 100 C. to a thick syrup. This syrup was coated onto a sheet of steel and heated at 100 C. until a clear, hard, polymer film was formed.

After the mixture was cooled, the product was Washed thoroughly Example 6 To a solution of 2,4,6-trinitrophenylethanol in '70 cc. of hot dry benzene, there was gradually added 7.5 grams of the acid chloride of fumaric acid mono-allyl ester,

dissolved in 20 cc. of dry benzene. The mixture was boiled for several hours, cooled, and the product washed with water, dilute sodium carbonate solution, and finally with water, then evaporated to dryness in vacuo. The residual oil was purified by-several washings with hot alcohol and finally'dried in vacuo at C. The trinitrophenylethyl allyl fumarate which was obtained polymerized when heated with benzoyl peroxide (1%) at C. to; a soft, pliable, non-tacky resin.

The corresponding maleate is obtained by heating one molecular equivalent each of maleic anhydride and 2,4 6-trinitrophenylethanol a 80 C. in benzene solution for several hours, then adding an excess of allyl alcohol, a small amount (1 cc.) of concentrated sulfuric acid, and refluxing until no more water is evolved, then cooling, Washing, and evaporating off the solvent. and excess allyl alcohol. It is a brown oil whichalso polymerizes as above to an explosive plastic.

We claim:

1. A readily combustible plastic polymer of an ester having the formula wherein R is a, nitro hydrocarbon radical having one to ten carbon atoms and containing at least One nitro group i'or eachfour carbon atoms present in said hydrocarbon radical, only one'nitro group being present on any single carbon atom thereof, and R is the hydrocarbon residue'of a monohydric ray-unsaturated primary aliphatic alcohol of not over four carbon atoms.

2. A resinous polymer-of 2,4-,6'-trinitrophenylethyl allyl maleate.

3. A resinouspolymer or 2-nitro"-2'-meth-yl propyl allyl maleate.

4. A resinous polymer of 1-nitro-isopropylallyl maleate.

HERMAN A. BRUSON. GEORGE B. BUTLER. 

